CN103894184B - A kind of high-specific surface area vanadium zinc system's modification denitrating catalyst and preparation method - Google Patents
A kind of high-specific surface area vanadium zinc system's modification denitrating catalyst and preparation method Download PDFInfo
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Abstract
The invention discloses a kind of high-specific surface area vanadium zinc system modification denitrating catalyst, the carrier of catalyst is TiO
2, TiO
2-SiO
2or containing TiO
2the one of multi-element, inorganic complex oxide kind, TiO
2that metatitanic acid is through H
2o
2intensification modification obtain; Catalyst carrier is shaping is honeycomb ceramic type; The active component of catalyst is by V
2o
5, ZnO and WO
3composition.The invention has the beneficial effects as follows: the preparation technology of catalyst adopts kneading dipping combined techniques, adds in catalyst, given play to Zn element substep the synergy of V and Zn and W and Zn, ensure that low temperature active and the high-temperature stability of catalyst; Metatitanic acid and H
2o
2the chemical process having individual interionic complexing to disperse again, improves specific area and the uniformity of metatitanic acid, is beneficial to lower one-step forming, avoids the titanium dioxide that industry is conventional simultaneously, reduces cost.
Description
Technical field
The present invention relates to a kind of denitrating catalyst, particularly a kind of high-specific surface area vanadium zinc system's modification denitrating catalyst and preparation method.
Background technology
Nitrogen oxide is the major pollutants in air, and it is not only the main reason of nitric acid type acid rain, and can also form photochemical fog in atmosphere, can also cause very large harm to animals and plants and human body simultaneously.
Noble metal is a kind of catalyst applied the earliest, mainly comprises Pt, Rh, Pd etc.Be applicable to the lower and occasion not easily promoted of flue-gas temperature, there is higher catalytic activity, have certain anti-SO
2and H
2the ability of O, but because such catalyst price is too expensive, serviceability temperature narrow scope, O in system
2having inhibitory action etc. to SCR reaction, there is restriction in extensive use.
Later stage develops Mn system continuously, the denitrating catalyst of Cu system, denitration activity still can, but due to anti-SO
2with vapour resistant ability, poor heat stability, fail industrially to be promoted.
Technology is the most ripe in the world at present, and the gas denitrifying technology be most widely used is selective catalytic reduction, and the efficiency that this technique not only removes nitrogen oxide is high, and does not almost have secondary pollution, is a kind of technology highly promoted.The general principle of SCR technology (SCR method) is with NH
3, CO, H
2, hydrocarbon etc. as reducing agent, at O
2under existent condition, optionally by NO
xbe reduced into N
2and H
2o.Wherein, with NH
3for the SCR technology of reducing agent is widely used because its denitration efficiency is high, its reaction equation is as follows:
4NH
3+4NO+O
2→4N
2+6H
2O
Most widely used in business in SCR technique is V series catalysts, and Activity and stabill is fine, but V belongs to toxicant, and subsequent treatment pollutes seriously, and serviceability temperature interval is narrow, and low temperature active is poor.Therefore reduce the consumption of V series catalysts, and ensure that the low temperature active of catalyst and high-temperature stability are problem demanding prompt solutions.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of long service life, active temperature interval is wide, and especially low temperature active is good, high-temperature stability is good, and preparation technology is simple, toxicity is little, steam-resistant and SO
2high-specific surface area vanadium zinc system's modification denitrating catalyst that ability is strong and preparation method.
For solving the problems of the technologies described above, the invention provides a kind of high-specific surface area vanadium zinc system modification denitrating catalyst, the carrier of described catalyst is TiO
2, TiO
2-SiO
2or containing TiO
2the one of multi-element, inorganic complex oxide kind, described TiO
2that metatitanic acid is through H
2o
2intensification modification obtain; Described catalyst carrier is shaping is honeycomb ceramic type; The active component of described catalyst is by V
2o
5, ZnO and WO
3composition.
Described high-specific surface area vanadium zinc system modification denitrating catalyst, is characterized in that, when described carrier is described TiO
2during carrier, described catalyst comprises the component of following mass content: described TiO
2mass content is 90-95%; Described V2O
5mass content is 0.5 ~ 1.53%; Described ZnO mass content is 2.7 ~ 5.43%; Described WO
3mass content is 5 ~ 8%.
When described carrier is described TiO
2-SiO
2during carrier, described catalyst comprises the component of following mass content: described TiO
2mass content is 65 ~ 75%, SiO
2mass content is 10 ~ 18%; V in described catalyst activity component
2o
5mass content is 0.5 ~ 1.53%, and described ZnO mass content is 2.7 ~ 5.43%; Described WO
3mass content is 5 ~ 14%.
When described carrier is the described multi-element, inorganic complex oxide containing TiO2, described catalyst comprises the component of following mass content: the mass content of described TiO2 is 60 ~ 70%; Described V
2o
5mass content be 0.5 ~ 1.53%; Described ZnO mass content is 2.7 ~ 5.43%; Described WO
3mass content be 5 ~ 14%; Described Al
2o
3mass content be 5 ~ 7% and/or described SiO
2mass content be 10 ~ 18%.
Described catalyst size is (50-300) × (50-300) × (300-1200) mm.
The present invention also provides the preparation method of a kind of high-specific surface area vanadium zinc system modification denitrating catalyst, comprises step:
(1), hydrogen peroxide modified support:
Hydrogen peroxide modification TiO
2carrier: metatitanic acid is raw material, through H
2o
2the modified drying of intensification, pulverize obtained X;
Or hydrogen peroxide modification TiO
2-SiO
2carrier: metatitanic acid is raw material, through H
2o
2modified with the appropriate SiO of intensification
2or metasilicic acid mixes obtained Y;
Or hydrogen peroxide modification contains TiO
2polynary inorganic oxide complexes carrier: metatitanic acid is raw material, through H
2o
2the modified and 2Al of intensification
2o
3-nH
2o or SiO
2in one or severally arbitrarily mix obtained Z;
(2), by ammonium metatungstate and zinc nitrate wiring solution-forming mix, set aside for use;
(3), get appropriate mixed material X, Y or Z in any one and add shaping assistant, adhesive, flexibilizer, NMF and expanding agent, then after the solution adding described step (2), mediate evenly, old 24h aftershaping is a, then carries out drying, roasting;
(4), by ammonium metavanadate, oxalic acid and zinc nitrate wiring solution-forming b, wherein ammonium metavanadate and oxalic acid mol ratio are 1:1, after placement a period of time is stable, described a prepared by described step (3) is dissolved in described solution b, after stirring dipping 2h, take out and carry out drying, roasting, obtained catalyst;
Its mass ratio of zinc nitrate added in the zinc nitrate added in described step (2) and described step (4) is 1:6-5:1.
Described shaping assistant is carboxymethyl cellulose, and described peptizing agent is polyacrylamide, and described flexibilizer is glass fibre, and described NMF is glycerine and described expanding agent is flour.
In described step 3), baking temperature is 30 ~ 90 DEG C, and drying time is 12 ~ 18h, and sintering temperature is 480 ~ 580 DEG C, and roasting time is 2 ~ 3h.
In described step 4), baking temperature is 100 ~ 120 DEG C, and drying time is 3h, and calcining heat is 480 ~ 580 DEG C, and calcination time is 2 ~ 3h.
The beneficial effect that the technical scheme that the embodiment of the present invention provides is brought is:
Adopt H
2o
2the metatitanic acid of modification is denitration catalyst carrier raw material, avoids use titanium dioxide, has saved production cost.Metatitanic acid and H
2o
2have the chemical process that individual interionic complexing disperses again, the particle diameter of metatitanic acid can diminish and evenly, improve specific area and the uniformity of metatitanic acid, be beneficial to lower one-step forming.
Method for preparing catalyst is new method, and catalyst adopts kneading dipping combined techniques, and first by W and Zn and the modified even aftershaping of metatitanic acid kneading, heat up after drying roasting dipping in the stabilizing solution of V and Zn.By the kneading of W and Zn before carrier is shaping, the while that W and Zn can being made finely dispersed inside and outside carrier, utilize the synergy of Zn and W can ensure the high-temperature stability of carrier, the dipping that heats up in the solution of V and Zn after shaping can ensure the low temperature high activity of catalyst; V and Zn is made into stabilizing solution, and the easily disperse of Zn element can be utilized the V of low content can be scattered on catalyst more uniformly, the dispersed high activity determining catalyst of V.The technique of this Zn of adding ensure that the dispersion of Zn inside and outside catalyst and synergistic performance.
Detailed description of the invention
Below in conjunction with embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1:
[1] 30g ammonium metatungstate and zinc nitrate 17g are made into stabilizing solution 150ml.
[2] get metatitanic acid 500g, add shaping assistant carboxymethyl cellulose 20g, add adhesive polyacrylamide 5g, add flexibilizer glass fibre 30g, add NMF glycerine 15g, add expanding agent flour 10g, then add step [1] and join 150ml solution, mediate evenly, extrusion molding after old 24h, then progressively heat up drying from 30 DEG C, is warming up to 90 DEG C after 18h, taking-up puts into Muffle furnace at 580 DEG C of roasting 2h, obtained a1.
[3] water absorption rate measuring a1 is 32.5%.
[4] take ammonium metavanadate 6.5g, zinc nitrate 17g, oxalic acid 9g, be dissolved in 135g water, be stirred to whole dissolving, after placement a period of time is stable, a1 be placed in stabilizing solution, stir dipping 2h, after thorough impregnation, take out carrier dry 3h at 100 DEG C, 580 DEG C of roasting 2h, obtained catalyst C1.
Catalyst size is 100*200*800.
Embodiment 2:
[1] in 1kg metatitanic acid, H is added
2o
2(30wt%) 280g, at 30 DEG C, constant temperature stirs 20min, is progressively warming up to 45 DEG C, continues to stir 20min, continues to stir 20min, be then warming up to 90 DEG C, be crushed to 200 orders stand-by after dry 2h after being then warming up to 60 DEG C.
[2] 30g ammonium metatungstate and zinc nitrate 17g are made into stabilizing solution 150ml.
[3] get crushed material 500g in step [1], add shaping assistant carboxymethyl cellulose 20g, add adhesive polyacrylamide 5g, add flexibilizer glass fibre 30g, add NMF glycerine 15g, add expanding agent flour 10g, then add step [2] and join 150ml solution, mediate evenly, extrusion molding after old 24h, then progressively heat up drying from 30 DEG C, is warming up to 90 DEG C after 18h, taking-up puts into Muffle furnace at 580 DEG C of roasting 2h, obtained a2.
[4] water absorption rate measuring a2 is 36.5%.
[5] take ammonium metavanadate 6.5g, zinc nitrate 17g, oxalic acid 9g, be dissolved in 146g water, be stirred to whole dissolving, after placement a period of time is stable, a2 be placed in stabilizing solution, stir dipping 2h, after thorough impregnation, take out carrier dry 3h at 100 DEG C, 580 DEG C of roasting 2h, obtained catalyst C2.
Catalyst size is 50*300*1000.
Embodiment 3:
[1] 60g ammonium metatungstate and zinc nitrate 34g are made into stabilizing solution 169ml.
[2] metatitanic acid 400g is got, add metasilicic acid 105g, be stirred to completely evenly, add shaping assistant carboxymethyl cellulose=20.2g, add adhesive polyacrylamide 5.05g, add flexibilizer glass fibre 30.3g, add NMF glycerine 15.15g, add expanding agent flour 10.1g, then add step [1] and join 169ml solution, mediate evenly, extrusion molding after old 24h, then progressively heat up drying from 30 DEG C, is warming up to 90 DEG C after 15h, taking-up puts into Muffle furnace at 520 DEG C of roasting 3h, obtained a3.
[3] water absorption rate measuring a3 is 30.3%.
[4] take ammonium metavanadate 3.25g, zinc nitrate 17g, oxalic acid 4.5g, be dissolved in 121g water, be stirred to whole dissolving, after placement a period of time is stable, a3 be placed in stabilizing solution, stir dipping 2h, after thorough impregnation, take out carrier dry 3h at 110 DEG C, 520 DEG C of roasting 3h, obtained catalyst C3
Catalyst size is 200*100*600.
Embodiment 4:
[1] in 1kg metatitanic acid, H is added
2o
2(30wt%) 280g, at 30 DEG C, constant temperature stirs 20min, is progressively warming up to 45 DEG C, continues to stir 20min, continues to stir 20min, be then warming up to 90 DEG C, be crushed to 200 orders stand-by after dry 2h after being then warming up to 60 DEG C.
[2] 60g ammonium metatungstate and zinc nitrate 34g are made into stabilizing solution 165ml.
[3] crushed material 400g in step [1] is got, add metasilicic acid 105g, be stirred to completely evenly, add shaping assistant carboxymethyl cellulose 20.2g, add adhesive polyacrylamide 5.05g, add flexibilizer glass fibre 30.3g, add NMF glycerine 15.15g, add expanding agent flour 10.1g, then add step [2] and join 165ml solution, mediate evenly, extrusion molding after old 24h, then progressively heat up drying from 30 DEG C, is warming up to 90 DEG C after 15h, taking-up puts into Muffle furnace at 520 DEG C of roasting 3h, obtained a4.
[4] water absorption rate measuring a4 is 38.3%.
[5] ammonium metavanadate 3.25g is taken, zinc nitrate 17g, oxalic acid 4.5g, be dissolved in 153g water, be stirred to whole dissolving, after placement a period of time is stable, a4 is placed in stabilizing solution, stirs dipping 2h, after thorough impregnation, take out carrier dry 3h at 110 DEG C, 520 DEG C of roasting 3h, obtained catalyst C4.
Catalyst size is 300*50*1200.
Embodiment 5:
[1] 75g ammonium metatungstate and zinc nitrate 34g are made into stabilizing solution 159ml.
[2] metatitanic acid 400g is got, add metasilicic acid 68g, add boehmite 45g, be stirred to completely evenly, add shaping assistant carboxymethyl cellulose 20.52g, add adhesive polyacrylamide 5.13g, add flexibilizer glass fibre 30.78g, add NMF glycerine 15.39g, add expanding agent flour 10.26g, add step [1] again and join 159ml solution, mediate evenly, extrusion molding after old 24h, then progressively heat up drying from 30 DEG C, after 12h, be warming up to 90 DEG C, take out and put into Muffle furnace at 480 DEG C of roasting 3h, obtained a5.
[3] water absorption rate measuring a5 is 33.3%.
[4] ammonium metavanadate 9.75g is taken, zinc nitrate 34g, oxalic acid 13.5g, be dissolved in 133g water, be stirred to whole dissolving, after placement a period of time is stable, a5 is placed in stabilizing solution, stirs dipping 2h, after thorough impregnation, take out carrier dry 3h at 120 DEG C, 480 DEG C of roasting 3h, obtained catalyst C5.
Catalyst size is 240*180*1100.
Embodiment 6:
[1] in 1kg metatitanic acid, H is added
2o
2(30wt%) 280g, at 30 DEG C, constant temperature stirs 20min, is progressively warming up to 45 DEG C, continues to stir 20min, continues to stir 20min, be then warming up to 90 DEG C, be crushed to 200 orders stand-by after dry 2h after being then warming up to 60 DEG C.
[2] 75g ammonium metatungstate and zinc nitrate 34g are made into stabilizing solution 164ml.
[3] crushed material 400g in step [1] is got, add metasilicic acid 68g, add boehmite 45g, be stirred to completely evenly, add shaping assistant carboxymethyl cellulose 20.52g, add adhesive polyacrylamide 5.13g, add flexibilizer glass fibre 30.78g, add NMF glycerine 15.39g, add expanding agent flour 10.26g, add step [2] again and join 164ml solution, mediate evenly, extrusion molding after old 24h, then progressively heat up drying from 30 DEG C, 90 DEG C are warming up to after 12h, taking-up puts into Muffle furnace at 480 DEG C of roasting 3h, obtained a6.
[4] water absorption rate measuring a6 is 39.3%.
[5] ammonium metavanadate 9.75g is taken, zinc nitrate 34g, oxalic acid 13.5g, be dissolved in 157g water, be stirred to whole dissolving, after placement a period of time is stable, a6 is placed in stabilizing solution, stirs dipping 2h, after thorough impregnation, take out carrier dry 3h at 120 DEG C, 480 DEG C of roasting 3h, obtained catalyst C6.
Catalyst size is 300*300*300.
Embodiment 7:
[1] in 1kg metatitanic acid, H is added
2o
2(30wt%) 280g, at 30 DEG C, constant temperature stirs 20min, is progressively warming up to 45 DEG C, continues to stir 20min, continues to stir 20min, be then warming up to 120 DEG C, be crushed to 200 orders stand-by after dry 2h after being then warming up to 60 DEG C.
[2] 30g ammonium metatungstate is made into stabilizing solution 150ml.
[3] get crushed material 500g in step [1], add shaping assistant carboxymethyl cellulose 20g, add adhesive polyacrylamide 5g, add flexibilizer glass fibre 30g, add NMF glycerine 15g, add expanding agent flour 10g, then add step [2] and join 150ml solution, mediate evenly, extrusion molding after old 24h, then progressively heat up drying from 30 DEG C, is warming up to 90 DEG C after 18h, taking-up puts into Muffle furnace at 580 DEG C of roasting 2h, obtained a7.
[4] water absorption rate measuring a7 is 36.5%.
[5] take ammonium metavanadate 6.5g, zinc nitrate 17g, oxalic acid 9g, be dissolved in 146g water, be stirred to whole dissolving, after placement a period of time is stable, a7 be placed in stabilizing solution, stir dipping 2h, after thorough impregnation, take out carrier dry 3h at 110 DEG C, 580 DEG C of roasting 2h, obtained catalyst C7.
Catalyst size is 220*180*1100.
Embodiment 8:
[1] in 1kg metatitanic acid, H is added
2o
2(30wt%) 280g, at 30 DEG C, constant temperature stirs 20min, is progressively warming up to 45 DEG C, continues to stir 20min, continues to stir 20min, be then warming up to 90 DEG C, be crushed to 200 orders stand-by after dry 2h after being then warming up to 60 DEG C.
[2] 60g ammonium metatungstate is made into stabilizing solution 165ml.
[3] crushed material 400g in step [1] is got, add metasilicic acid 105g, be stirred to completely evenly, add shaping assistant carboxymethyl cellulose 20.2g, add adhesive polyacrylamide 5.05g, add flexibilizer glass fibre 30.3g, add NMF glycerine 15.15g, add expanding agent flour 10.1g, then add step [2] and join 165ml solution, mediate evenly, extrusion molding after old 24h, then progressively heat up drying from 30 DEG C, is warming up to 90 DEG C after 15h, taking-up puts into Muffle furnace at 520 DEG C of roasting 2h, obtained a8.
[4] water absorption rate measuring a8 is 38.3%.
[5] ammonium metavanadate 3.25g is taken, zinc nitrate 17g, oxalic acid 4.5g, be dissolved in 153g water, be stirred to whole dissolving, after placement a period of time is stable, a8 is placed in stabilizing solution, stirs dipping 2h, after thorough impregnation, take out carrier dry 3h at 110 DEG C, 520 DEG C of roasting 2h, obtained catalyst C8.
Catalyst size is 260*240*1100.
Embodiment 9:
[1] in 1kg metatitanic acid, H is added
2o
2(30wt%) 280g, at 30 DEG C, constant temperature stirs 20min, is progressively warming up to 45 DEG C, continues to stir 20min, continues to stir 20min, be then warming up to 90 DEG C, be crushed to 200 orders stand-by after dry 2h after being then warming up to 60 DEG C.
[2] 75g ammonium metatungstate is made into stabilizing solution 164ml.
[3] crushed material 400g in step [1] is got, add metasilicic acid 68g, add boehmite 45g, be stirred to completely evenly, add shaping assistant carboxymethyl cellulose 20.52g, add adhesive polyacrylamide 5.13g, add flexibilizer glass fibre 30.78g, add NMF glycerine 15.39g, add expanding agent flour 10.26g, add step [2] again and join 164ml solution, mediate evenly, extrusion molding after old 24h, then progressively heat up drying from 30 DEG C, 90 DEG C are warming up to after 12h, taking-up puts into Muffle furnace at 480 DEG C of roasting 3h, obtained a9.
[4] water absorption rate measuring a9 is 39.3%.
[5] ammonium metavanadate 9.75g is taken, zinc nitrate 34g, oxalic acid 13.5g, be dissolved in 157g water, be stirred to whole dissolving, after placement a period of time is stable, a9 is placed in stabilizing solution, stirs dipping 2h, after thorough impregnation, take out carrier dry 3h at 110 DEG C, 480 DEG C of roasting 3h, obtained catalyst C9.
Catalyst size is 280*200*1000.
Table 1 catalyst components is containing scale (%)
| V 2O 5 | ZnO | WO 3 | Al 2O 3 | SiO 2 | TiO 2 | |
| C1 | 1.05 | 2.7 | 5.51 | - | - | 90.74 |
| C2 | 1.06 | 2.7 | 5.51 | - | - | 90.73 |
| C3 | 0.51 | 4.05 | 11.2 | - | 16.8 | 67.24 |
| C4 | 0.50 | 4.06 | 11.1 | - | 16.7 | 67.64 |
| C5 | 1.53 | 5.43 | 13.95 | 5.8 | 11.1 | 62.19 |
| C6 | 1.52 | 5.42 | 13.94 | 5.79 | 11.2 | 62.13 |
| C7 | 1.06 | - | 5.51 | - | - | 93.43 |
| C8 | 0.50 | - | 11.1 | - | 16.7 | 71.4 |
| C9 | 1.52 | - | 13.94 | 6.01 | 10.9 | 67.54 |
Comprehensive above embodiment: wherein C1, C3, C5 are be the catalyst of carrier without the metatitanic acid of hydrogen peroxide modification.Wherein C2, C4, C6 be through the metatitanic acid of hydrogen peroxide modification be the catalyst of carrier.Wherein C7, C8, C9 are for being carrier through hydrogen peroxide modification metatitanic acid, but do not add the catalyst of auxiliary agent Zn.
Table 2 catalyst physical performance
| Catalyst | Breaking strength (N/cm) | Pore volume (ml/g) | Specific area (m 2/g） |
| C1 | 79 | 0.259 | 53.7 |
| C2 | 89 | 0.294 | 79.3 |
| C3 | 85 | 0.272 | 57.4 |
| C4 | 94 | 0.311 | 82.7 |
| C5 | 89 | 0.281 | 58.8 |
| C6 | 102 | 0.321 | 84.3 |
| C7 | 88 | 0.292 | 79.3 |
| C8 | 95 | 0.313 | 82.6 |
| C9 | 100 | 0.322 | 84.1 |
By the above-mentioned data of C1 and C2 in contrast table 2, C3 and C4 and C5 and C6, can significantly find out, be that the specific area of the catalyst of carrier and pore volume are significantly improved compared to the catalyst without hydrogen peroxide modification through the metatitanic acid that hydrogen peroxide is modified, specific area promotes about 47%, meets the requirement of denitrating catalyst for specific area and pore volume completely.And metatitanic acid is cheap compared to conventional titanium dioxide, therefore substitutes titanium dioxide with modified metatitanic acid and will bring huge cost advantage.
Table 3 catalyst activity evaluation (%)
| Catalyst | 180℃ | 240℃ | 280℃ | 320℃ | 360℃ | 400℃ | 440℃ | 480℃ |
| C1 | 72.3 | 80.4 | 83.7 | 87.5 | 88.3 | 83.4 | 80.2 | 79.2 |
| C2 | 85.7 | 92.4 | 95.8 | 99.3 | 99.5 | 95.2 | 90.1 | 89.3 |
| C3 | 70.4 | 73.6 | 77.9 | 80.5 | 84.6 | 80.4 | 76.4 | 75.3 |
| C4 | 82.7 | 87.9 | 91.6 | 93.7 | 96.2 | 93.7 | 88.7 | 87.6 |
| C5 | 71.9 | 76.7 | 80.9 | 84.8 | 86.8 | 82.1 | 79.2 | 77.5 |
| C6 | 84.1 | 91.8 | 94.7 | 97.3 | 97.8 | 94.6 | 89.3 | 88.4 |
| C7 | 67.3 | 78.6 | 86.6 | 92.3 | 95.6 | 90.2 | 85.6 | 64.8 |
| C8 | 62.9 | 73.9 | 80.7 | 89.3 | 93.2 | 84.7 | 82.6 | 61.2 |
| C9 | 65.3 | 74.6 | 83.6 | 90.9 | 93.9 | 85.9 | 83.7 | 64.6 |
By the above-mentioned data of C1 and C2 in contrast table 3, C3 and C4 and C5 and C6, can find out, through the modified catalyst of hydrogen peroxide because specific area and pore volume all increase, active component on catalyst and the contact of flue gas more abundant, catalyst activity is higher, data significantly can find out by modification metatitanic acid to be the denitrating catalyst excellent performance of carrier by experiment, and catalytic activity is high.
By the above-mentioned data of C2 and C7 in contrast table 3, C4 and C8 and C6 and C9, can find out: by the kneading of W and Zn before carrier is shaping, the while that W and Zn can being made finely dispersed inside and outside carrier, utilize the synergy of Zn and W can ensure the high-temperature stability of carrier, after shaping, in the solution of V and Zn, dipping can ensure the low temperature high activity of catalyst; V and Zn is made into stabilizing solution, and the easily disperse of Zn element can be utilized the V of low content can be scattered on catalyst more uniformly, the dispersed high activity determining catalyst of V.The technique of this Zn of adding ensure that the dispersion of Zn inside and outside catalyst and synergistic performance.
Table 4SO
2add on catalyst activity impact (%)
| Catalyst | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 |
| Illogical SO 2 | 98.3 | 99.5 | 94.6 | 96.2 | 96.8 | 97.8 | 95.6 | 92.2 | 92.9 |
| Pass into SO 2 | 97.6 | 98.9 | 92.8 | 94.1 | 92.1 | 92.9 | 93.4 | 86.7 | 82.9 |
| Fading rate | 0.7 | 0.6 | 1.8 | 2.1 | 4.8 | 5 | 2.2 | 5.5 | 8.0 |
Adding of table 5 water vapour affects catalyst activity
| Catalyst | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 |
| Illogical H 2O | 98.3 | 99.5 | 94.6 | 96.2 | 96.8 | 97.8 | 95.6 | 92.2 | 92.9 |
| Pass into H 2O | 97.2 | 98.6 | 93.2 | 94.9 | 95.5 | 96.4 | 90.7 | 87.4 | 87.3 |
| Fading rate | 1.1 | 0.9 | 1.4 | 1.3 | 1.3 | 1.4 | 4.9 | 4.8 | 5.6 |
The evaluation temperature of table 4 and table 5 is 360 DEG C.
As can be seen from Table 4, improve the anti-SO of catalyst adding of Zn-ef ficiency
2ability, adding of aluminium element silicon is vanadium catalysis SO
2provide carrier, do not promote the activity of catalyst further.。
As can be seen from Table 5, adding of Zn-ef ficiency, improve catalyst steam-resistant ability, catalytic activity does not have large decline, and without the catalyst of zinc, activity has certain decline.
The new preparation process of catalyst adopts kneading dipping combined techniques, and first by W and Zn and the modified even aftershaping of metatitanic acid kneading, heat up after drying roasting dipping in the stabilizing solution of V and Zn.By the kneading of W and Zn before carrier is shaping, the while that W and Zn can being made finely dispersed inside and outside carrier, utilize the synergy of Zn and W to ensure the high-temperature stability of carrier, after shaping, in the solution of V and Zn, dipping can ensure the low temperature high activity of catalyst; V and Zn is made into stabilizing solution, and the easily disperse of Zn element can be utilized the V of low content can be scattered on catalyst more uniformly, the dispersed high activity determining catalyst of V.The technique of this Zn of adding ensure that the dispersion of Zn inside and outside catalyst and synergistic performance.
The carrier of catalyst adopts the metatitanic acid of domestic low specific surface area to be raw material, cheap and easy to get; Metatitanic acid through hydrogen peroxide modification, metatitanic acid and H
2o
2have the chemical process that individual interionic complexing disperses again, the particle diameter of metatitanic acid diminishes and evenly, improves specific area and the uniformity of metatitanic acid, be beneficial to lower one-step forming.
Catalyst carrier is shaping is honeycomb ceramic type, adds edible flour in forming process, and instead of the expanding agents such as conventional active carbon, flour is cheap and easy to get, and flour is decomposed into CO after roasting
2and water, complete decomposition is pollution-free, expands pore volume and the specific area of catalyst simultaneously.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. a high-specific surface area vanadium zinc system modification denitrating catalyst, is characterized in that, the carrier of described catalyst is TiO
2, TiO
2-SiO
2or containing TiO
2the one of multi-element, inorganic complex oxide kind, described TiO
2that metatitanic acid is through H
2o
2intensification modification obtain; Described catalyst carrier is shaping is honeycomb ceramic type; The active component of described catalyst is by V
2o
5, ZnO and WO
3composition;
The preparation method of described high-specific surface area vanadium zinc system modification denitrating catalyst, comprises step:
(1), hydrogen peroxide modified support:
Hydrogen peroxide modification TiO
2carrier: metatitanic acid is raw material, through H
2o
2the modified drying of intensification, pulverize obtained X;
Or hydrogen peroxide modification TiO
2-SiO
2carrier: metatitanic acid is raw material, through H
2o
2modified with the appropriate SiO of intensification
2or metasilicic acid mixes obtained Y;
Or hydrogen peroxide modification contains TiO
2polynary inorganic oxide complexes carrier: metatitanic acid is raw material, through H
2o
2the modified and 2Al of intensification
2o
3nH
2o or SiO
2in one or severally arbitrarily mix obtained Z;
(2), by ammonium metatungstate and zinc nitrate wiring solution-forming mix, set aside for use;
(3), get appropriate mixed material X, Y or Z in any one and add shaping assistant, adhesive, flexibilizer, NMF and expanding agent, then after the solution adding described step (2), mediate evenly, old 24h aftershaping is a, then carries out drying, roasting;
(4), by ammonium metavanadate, oxalic acid and zinc nitrate wiring solution-forming b, wherein ammonium metavanadate and oxalic acid mol ratio are 1:1, after placement a period of time is stable, described a prepared by described step (3) is dissolved in described solution b, after stirring dipping 2h, take out and carry out drying, roasting, obtained catalyst;
Its mass ratio of zinc nitrate added in the zinc nitrate added in described step (2) and described step (4) is 1:6-5:1.
2. high-specific surface area vanadium zinc system according to claim 1 modification denitrating catalyst, is characterized in that, when described carrier is described TiO
2during carrier, described catalyst comprises the component of following mass content: described TiO
2mass content is 90-95%; Described V
2o
5mass content is 0.5 ~ 1.53%; Described ZnO mass content is 2.7 ~ 5.43%; Described WO
3mass content is 5 ~ 8%; The total amount of the mass content of described each component is 100%.
3. high-specific surface area vanadium zinc system according to claim 1 modification denitrating catalyst, is characterized in that, when described carrier is described TiO
2-SiO
2during carrier, described catalyst comprises the component of following mass content: described TiO
2mass content is 65 ~ 75%, SiO
2mass content is 10 ~ 18%; Described V
2o
5mass content is 0.5 ~ 1.53%, and described ZnO mass content is 2.7 ~ 5.43%; Described WO
3mass content is 5 ~ 14%.
4. high-specific surface area vanadium zinc system according to claim 1 modification denitrating catalyst, is characterized in that, when described carrier is described containing TiO
2multi-element, inorganic complex oxide time, described catalyst comprises the component of following mass content: described TiO
2mass content be 60 ~ 70%; Described V
2o
5mass content be 0.5 ~ 1.53%; Described ZnO mass content is 2.7 ~ 5.43%; Described WO
3mass content be 5 ~ 14%; Al
2o
3mass content be 5 ~ 7% and/or SiO
2mass content be 10 ~ 18%; The total amount of the mass content of described each component is 100%.
5., according to the arbitrary described high-specific surface area vanadium zinc system modification denitrating catalyst of claim 1-4, it is characterized in that, described catalyst size is (50-300) × (50-300) × (300-1200) mm.
6. high-specific surface area vanadium zinc system according to claim 1 modification denitrating catalyst, it is characterized in that, described shaping assistant is carboxymethyl cellulose, and described adhesive is polyacrylamide, described flexibilizer is glass fibre, and described NMF is glycerine and described expanding agent is flour.
7. high-specific surface area vanadium zinc system according to claim 1 modification denitrating catalyst, is characterized in that: in described step (3), baking temperature is 30 ~ 90 DEG C, and drying time is 12 ~ 18h, and sintering temperature is 480 ~ 580 DEG C, and roasting time is 2 ~ 3h.
8. high-specific surface area vanadium zinc system according to claim 1 modification denitrating catalyst, is characterized in that: in described step (4), baking temperature is 100 ~ 120 DEG C, and drying time is 3h, and calcining heat is 480 ~ 580 DEG C, and calcination time is 2 ~ 3h.
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| CN105618028A (en) * | 2014-11-02 | 2016-06-01 | 中国科学院大连化学物理研究所 | Catalyst for coke oven smoke denitration and preparation method thereof |
| CN104785246B (en) * | 2015-04-13 | 2017-06-23 | 国电环境保护研究院 | Manganese cerium support type low-temperature SCR catalyst preparation method based on titanyl hydroxide starting material |
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| CN102335603A (en) * | 2011-07-20 | 2012-02-01 | 中电投远达环保工程有限公司 | Denitrification catalyst capable of oxidizing simple substance mercury |
| CN102896002A (en) * | 2012-10-10 | 2013-01-30 | 浙江海亮环境材料有限公司 | Method for preparing titanium dioxide-tungsten trioxide (TiO2-WO3) composite powder |
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| CN102335603A (en) * | 2011-07-20 | 2012-02-01 | 中电投远达环保工程有限公司 | Denitrification catalyst capable of oxidizing simple substance mercury |
| CN102896002A (en) * | 2012-10-10 | 2013-01-30 | 浙江海亮环境材料有限公司 | Method for preparing titanium dioxide-tungsten trioxide (TiO2-WO3) composite powder |
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